Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/02—Photosensitive materials characterised by the image-forming section
  • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
  • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors
  • G03C8/12—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors characterised by the releasing mechanism
  • G03C8/22—Reduction of the chromogenic substance
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B29/00—Monoazo dyes prepared by diazotising and coupling
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B43/00—Preparation of azo dyes from other azo compounds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/156—Precursor compound
  • Y10S430/159—Development dye releaser, DDR

Definitions

• the invention relates to a photographic recording material for the production of photographic images by the diffusion transfer process and to novel compounds which can release a photographically active residue.
• the photographically effective residue can be a dye or a dye precursor.
• coloring compounds the non-diffusing Farbkup described in German Patent 1,095,115, for example, p ler to count that in Set development as a result of reaction with the oxidation product of a group consisting of an aromatic primary amine color developing agent a preformed or in Farbkup dye lung p produced in diffusible form in freedom.
• the selection of the developer compound required is naturally limited to color developers.
• non-diffusing coloring compounds described in DE-OS 1 930 215, which contain a pre-formed latent diffusible dye residue linked to a diffusion-proofing residue via a cleavable hydrazone group.
• These compounds are not to be called color couplers, and it has also been found that the choice of developer compounds which are required to release the diffusing dye residue is in no way limited to the usual color developers, but that black and white developers, e.g. Catechins are very useful.
• DE-OS 1 772 929 also describes non-diffusing colored compounds with a special grouping which undergo an oxidative ring closure reaction during development and thereby release a pre-formed dye residue in diffusing form.
• the connections presented there can be divided into two groups.
• the compounds of the one group require a customary color developer compound for development, with whose oxidation product they couple and in a subsequent ring closure reaction release the pre-formed dye residue in a diffusing form.
• the compounds of the other group are themselves silver halide developing agents and are therefore able, even in the absence of further developer compounds in the oxidized form, to undergo the aforementioned ring closure reaction with the release of the diffusing dyes.
• non-diffusing coloring compounds of DE-OS 2 242 762 should also be mentioned at this point.
• These are sulfonamidophenols and sulfonamidoanilines which, after the oxidation which has occurred during development, release a diffusing dye under the influence of the developer alkali with the release of diffusing dyes Sulfamoyl group are cleaved.
• the coloring compounds mentioned above work without exception negative, i.e. the image-wise distribution of the diffusing dye released arises when conventional (negative working) silver halide emulsions are used in accordance with the negative silver image produced during development. In order to generate positive dye images, it is therefore necessary to use direct-positive silver halide emulsions or else to use a suitable reversal process.
• non-diffusing oxidizable coloring compounds are known from DE-OSes 2 402 900, 2 543 902, 2 823 159 and US Pat. Nos. 3,980,479, 4,108,850 and GB Patents 1 464 105 and 1 464 104. in the reduced form are capable of a cleavage reaction under alkaline development conditions, a diffusing dye being released, and in which on the other hand the above-mentioned cleavage reaction is made difficult or prevented in oxidized form.
• Such compounds in combination with conventional negative emulsions, are suitable for producing positive transfer color images.
• Such compounds are described in DE-OS 2 809 716 and DE-OS 2 809 857; they contain an electron-accepting nucleophilic precursor group which has to be reduced in order to be able to enter into an intramolecular nucleophilic displacement reaction with the release of a photographically effective residue.
• the published European patent application 4399 describes reducible compounds with an electron accepting group which must be reduced in order to be able to release a photographically active residue from the reducible compound in an elimination reaction.
• a new class of non-diffusing compounds has now been found which are reducible and, in reduced form, are subject to a cleavage reaction under the influence of the developer alkali with the release of a photographically active group, in particular a diffusing dye, but which do the cleavage mentioned are not subject to the reaction or only to a much lesser extent if they are not reduced.
• the compounds of the present invention have a reducible group and a further group which can be converted (activated) into an active state by reducing the first group so that they undergo an intramolecular nucleophilic displacement reaction or a 1,4- or 1,6- Elimination reaction is received, a photographically active residue being released from the (reduced form of) the reducible compound according to the invention.
• the present invention relates to a photographic recording material with at least one light-sensitive silver halide emulsion layer and a non-diffusing compound associated therewith which, in reduced form, is subject to a cleavage reaction under the conditions of alkaline development with the release of a photographically active group, e.g. of a diffusing dye, and which is not, or only to a much lesser extent, subject to the cleavage reaction mentioned than in a reduced form.
• a photographically active group e.g. of a diffusing dye
• the non-diffusing compounds are referred to below as coloring compounds.
• An acyl group represented by W or R 2 is derived from aliphatic or aromatic carbon ,. Sulfinic or sulfonic acids, or of carbonic acid or carbonic acid semi-esters, or of carbamic or sulfamic acid; the latter can be mono- or disubstituted on the nitrogen atom by alkyl, aryl or heterocyclic groups. Examples are alkylsulfonyl groups, N-alkylsulfamoyl groups and N-alkylcarbamoyl groups.
• An acyl group represented by R 2 is in particular one which can easily be hydrolyzed under the alkaline development conditions, so that the group -XH or -X 8 in free form for the subsequent intramolecular nucleophilic displacement reaction, 1,4- or 1,6 -Eliminating reaction or otherwise Ab cleavage reaction is available.
• hydrolyzable acyl groups are preferably acyl groups derived from carboxylic acids or carbonic acid semiesters, in particular the acetyl group, the chlorine, dichloro or trichloroacetyl group, the trifluoroacetyl group, the pyruvyl group, the toluyl group, the p-methoxybenzoyl group and the ethoxycarbonyl group.
• the substituent E is preferably arranged in such a way that its reduction results in optimal activation of the group -XR 2 ; if, for example, R 0 is the radical to complete a 6-membered ring, E is preferably in the o- or p-position to - XR 2 . If R 2 is an acyl radical, its hydrolysis is difficult as long as E is in the unreduced form. Reduction of E results in a significant acceleration of the hydrolytic cleavage of the acyl radical R 2 if XR 2 is in the o-position to E.
• the substituent W is preferably arranged so that it reduces the electron density in the position of the substituent E; if R 0 completes the rest of a 6-membered ring, W is preferably in the o- or p-position to E.
• the radical A denotes a photographically active radical
• Photographically effective residues are, for example, dyes, dye precursors, couplers, for example DIR couplers, mask couplers, white couplers, stabilizers, development inhibitors and bleaching accelerators.
• the compounds according to the invention are particularly suitable for the production of photographic color images, preference is given to those compounds in which A denotes a dye-forming radical.
• A can represent a finished pre-formed dye or a dye precursor product.
• the residues of dyes of all dye classes are suitable as residues insofar as they are sufficiently diffusible to be able to diffuse through the layers of the light-sensitive material into the image-receiving layer.
• the dye residues can be provided with one or more water-solubilizing groups. Suitable water-solubilizing groups include carboxyl groups, sulfo groups, sulfonamide groups and aliphatic or aromatic hydroxyl groups.
• dyes which are particularly suitable for the process according to the invention are: azo dyes, azomethine dyes, anthraquinone dyes, phthalocyanine dyes, indigoid dyes, triphenylmethane dyes, including those dyes which are complexed or complexable with metal ions.
• Suitable dye residues are described, for example, in DE-OS 2 242 762, DE-OS 2 505 248 and in Research Disclosure 15 654 (April 77). Reference is also made to the German laid-open publications 2 626 821 and 2 756 656 for yellow image dyes, 2 406 626, 2 406 627 and 2 503 443 for purple dyes and 2 406 653, 2 462 010 and 2 607 440 for blue-green image dyes.
• Suitable metallizable dyes as photographically active residues for the non-diffusing reducible compounds according to the invention are described in US Pat. Nos. 4,165,238, 4,165,987, 4,183,754 and 4,183,755.
• the residues of dye precursor products are to be understood as the residues of such compounds which, in the course of photographic processing, are carried out by customary or additional processing steps, whether by means of oxides tion, be it by coupling or by exposure of an auxochromic group in a chromophoric system, for example by saponification, to be converted into dyes.
• Dye precursors in this sense can be leuco dyes, couplers or dyes that are converted into other dyes during processing, for example so-called "shifted dyes".
• shifted dyes are understood to mean those in which the further absorption shifts hypsochromically or bathochromically when the dyes are subjected to a change in the environment, e.g. a change in pH or be changed chemically, e.g. by formation of metal complexes or the elimination of a substituent from the chromophoric system of the dye, as described in US Pat. No. 3,260,597.
• the "shifted dyes” are advantageous because their absorption areas are initially outside the photosensitivity range of the associated silver halide emulsions, so that no reduction in photosensitivity is possible. Only in the course of processing, e.g. in the image-receiving layer, these dyes are converted into those which absorb in the desired absorption range of the image dyes by the action options mentioned.
• the bivalent link Y which may be the Diffusion rate of the remainder A controls and influences the cleavage rate, can in particular correspond to the following formulas:
• coloring compounds according to the invention should not diffuse as intact molecules in the layers of the photographic material.
• they contain a diffusion-proofing residue, e.g. in one of the substituents mentioned or in a condensed ring.
• Adequate diffusion resistance of the coloring compounds can itself be provided if the substituents mentioned do not contain any longer alkyl radicals, since the molecule can also have a sufficient size, depending on the dye radical. Otherwise there is the possibility of making the coloring compounds diffusion-resistant by selecting residues of a suitable size.
• R 0 is the radical to complete a 6-membered aromatic ring. to which further rings can be condensed. Particularly preferred rings are the benzene and naphthalene rings.
• the compounds of formula I can be obtained by processes known per se. It can be assumed that chlorophenols are processed according to the following scheme.
• the chlorophenols used as starting materials are known from the literature.
• the acylation (1) of these compounds takes place according to the usual methodology with an acid scavenger in aprotic solvents.
• the introduced acyl group can be rearranged according to (2) by a Fries shift (cf. Org. Reactions, 1 (1942), 342-369).
• the introduction of the substituent E (3) usually proceeds easily from the activated aromatics [vg1. e.g. Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume X / 1, page 606; M. Krause: Reports of the German Chemical Society 32 (1899), 1247.
• the substituent W (4) is introduced by replacing the halogen atom with e.g. a mercaptan and oxidation of the thioether obtained using hydrogen peroxide.
• the implementation according to (5a) is known from the organic, 1967, page 488, the reaction according to (5b) from JACS 73 (1951), 2857 and JACS 74 (1952), 3668.
• the last reaction step (6) for obtaining the compounds according to the invention is known from Hinsberg, Ber. 50 (1917), 468 and Balfe, J.Chem.Soc. (1950), 3309, as well as the u. U. advantageous acylation reaction.
• the compound no longer has a sharp melting point but decomposes at 220 - 230 ° C.
• the double acylated, yellow product is obtained in good purity.
• the substituents shown in formula I can be in a wide variety of positions. However, they are preferably in positions in which an organic ring or a comparatively short-lived organic ring can easily form as a result of the intramolecular reaction of the group XR 2 with G or in which XR 2 together with the group GR 1 forms a 1,4- or 1 , 6-Elimination can go.
• R 2 and R 1 are split off to form a new ⁇ bond and shift at least one existing ⁇ electron pair. This reaction takes place after the radical E has taken up at least one electron; the rate of this reaction before the reduction of group E is extremely slow or practically zero.
• novel compounds of the invention are those which are stable under processing or development conditions, except when the release of a compound occurs as a direct function of the reduction in group E.
• the compounds can also have other groups which ionize or hydrolyze.
• the primary imagewise release of the photographically active compound takes place through the reactions mentioned above, the group which has been obtained by reduction of group E influencing group XR 2 in such a way that the reactions described for cleaving off the photographically active radical begin .
• the compounds according to the invention are used under comparatively strongly alkaline conditions, then the different groups of the compounds are selected such that the compounds are comparatively stable to external attack by alkali.
• the compounds according to the invention offer several advantages over comparable known compounds of the prior art.
• An essential advantage of the compounds according to the invention over corresponding oxidizable compounds is that they have to accept electrons, ie they have to undergo a reduction before the photographically active compound can be released.
• the compounds according to the invention are comparatively stable in a wide variety of liquid media, such as, for example, alkaline media.
• the known compounds must be oxidized before they are subject to a release mechanism or they hydrolyze to release a compound as a function of pH rather than as a result of a reduction.
• the compounds of the present invention offer the advantage that in the cleavage-causing reaction chain in addition to the reduction of the group E with the hydrolytic cleavage of the group -X-R with formation of the corresponding group -XH or - X e is an further partial reaction is available, which must take place before the photographically active compound can be released. This can have a favorable effect on the haze behavior, for example.
• the compounds of the invention are reacted with an electron donor compound (ED compound) which reduces the radical E to form a group which increases the reactivity of the group -XR 2 together with GR 1 in comparison with the starting compound according to the invention so that it R 1 is released.
• ED compound electron donor compound
• the ED connection can be supplied to the connection according to the invention, for example, by spraying on by means of a template, by physical transmission, by suction or by image-wise transmission.
• the compounds according to the invention are preferably used in combination with suitable ED compounds in photographic layers in order to release the diffusible, photographically active compound imagewise by reductive cleavage.
• the ED compound is then oxidized imagewise at the exposed areas and thereby inactivated before it can react with the compound according to the invention. In this way, the image reversal is achieved in the reductive cleavage of the compound according to the invention.
• An ED compound is generally understood to mean such a compound which can reduce the compounds according to the invention and thereby activate them to split off the photographically active group.
• Suitable ED compounds are described, for example, in DE-OS 2 809 716 and in German patent application P 29 47 425.7.
• so-called ED precursor connections are used as ED connections. These are generally understood to mean those compounds which contain the reduction-active function required for the reductive cleavage of the compounds according to the invention in chemically capped form. Only at certain pH values are the ED precursor compounds converted into ED compounds, which are then only able to react with the compound according to the invention. This results in a further time differentiation of the reaction processes and thus improved possibilities for controlling the entire mechanism. Suitable ED precursor compounds are the subject of German patent application P 30 06 268.1.
• the ED compounds or ED precursor compounds are preferably introduced into the photographic material or the photographic material is constructed in such a way that they can only be effective for the formation of the respective partial color image.
• a photographic recording material for producing color images in true-to-life colors accordingly contains three layer units for producing the three partial color images, namely a layer unit with a blue-sensitive silver halide emulsion layer and means for producing the yellow partial color image, a layer unit with a green-sensitive silver halide emulsion layer and means for producing the purple-colored partial color image and finally a layer unit with a red-sensitive silver halide emulsion layer and means for Er generation of the blue-green partial color image.
• the ED connections or ED precursor connections are now used in such a way that they are only effective in the shift unit assigned to them. This can be achieved, for example, in that the layer units in question are separated by intermediate layers which contain connections for intercepting the ED connections or ED precursor connections.
• Another possibility of restricting the action of the ED compounds or ED precursor compounds to the layer unit in question is to store these compounds in a diffusion-resistant form. This is achieved with the usual means, for example by substitution with ballast groups, generally long-chain alkyl radicals, or by incorporation in heterodisperse form, dissolved in what are known as oil formers. The technology required for this is known from the incorporation of color couplers into conventional color photographic materials.
• the ED compound used 'or reacts with the use of ED-precursor compounds, the resulting under alkaline conditions thereof ED compound immediately with the oxidized photographic developer and loses the ability to cleave the compound of the invention by reduction. The oxidized developer substance is thereby reduced and is thus available again for the development of further exposed halogen silver.
• the ED compound (which optionally arises hydrolytically from the ED precursor compound) reacts immediately with the compound according to the invention with reductive cleavage and formation of the diffusible, photographically active compound, advantageously an image dye.
• ED compound or ED precursor compound on the one hand and the compound according to the invention on the other hand can either be incorporated in separate solutions; in many cases, however, it is advantageous to incorporate the ED compound or ED precursor compound together with the compound according to the invention, so that these two reactants are contained together in the droplets of the oil former.
• concentration of the ED compounds or the ED precursor compounds in the layer units of the photographic material can vary within wide limits. In general, there have been concentration ratios of the ED compound or ED precursor compound to the compound according to the invention from 1: 2 to 2: 1, preferably 1: 1 to 2: 1, have been found to be useful.
• the non-diffusing, reducible compounds according to the invention are incorporated into the casting solutions for the layers of the photographic material by one of the customary methods.
• the amount of non-diffusing, reducible compound used per liter of casting solution varies within relatively wide limits, the most favorable concentration being determined on the basis of simple experiments. For example, 5 to 80 g, preferably 20 to 40 g, of reducible compound are used per liter of casting solution.
• non-diffusing reducible compound and silver halide required to achieve the desired effect can be made, for example, by introducing the compounds according to the invention from the aqueous solution into the casting solutions using existing strongly acidic water-solubilizing groups.
• the non-diffusing, reducible compounds can, however, also be introduced into the layers by one of the known emulsification processes. Such methods are described, for example, in English Patents 791 219 and 1 099 414 to 1 099 417. It is also possible to prepare aqueous dispersions of the reducible compounds and to add them to the respective casting solutions.
• aqueous slurries of the reducible compound are fine, for example by intensive stirring with the addition of sharp-edged sand or by using ultrasound grind.
• the non-diffusing reducible compounds can be accommodated in a light-sensitive layer itself or in a neighboring layer.
• the red-sensitive layer is, for example, a compound which cleaves off a blue-green dye and the green-sensitive layer is a one. purple dye-releasing compound and the blue-sensitive layer is assigned a yellow dye-releasing compound.
• Compounds according to the invention which contain diffusible, photographically active residues other than image dye-forming agents, are added to the photographic materials in a manner similar to color-imparting compounds according to the invention, ie depending on the type of the photographically active residue either in the light-sensitive silver halide emulsion layer or in layers adjacent to it. Depending on the function and the desired effect, concentrations of preferably 0.01 to 10 g / m 2 can be used. In the case of development inhibitors or stabilizers as photographically active, diffusible residues, the compounds according to the invention are used in the photographic material in such a way that they can act in contact with the silver halide emulsions.
• the development inhibitor or the stabilizer is then released in a pictorial distribution at the unexposed areas.
• the formation of developed silver in the little or unexposed layer areas is effectively suppressed. Since the formation of developed silver by deactivating the ED compounds or ED precursors bindings suppresses the formation of dyes, the simultaneous use of coloring compounds according to the invention and compounds according to the invention which release development inhibitors favors dye formation at the unexposed areas and thereby increases the image dye density.
• the developer compounds essentially have the function of developing the imagewise exposed silver halide and, in imagewise agreement with the developed silver halide, of oxidizing the ED compound and thereby removing it from the subsequent reaction with the compounds according to the invention.
• the usual photographic developers are generally suitable as developer or auxiliary developer compounds, e.g. Hydroquinone or derivatives thereof such as 2,5-dichlorohydroquinone and 2-chlorohydroquinone; Aminophenol compounds such as 4-aminophenol, N-methylaminophenol, 3-methyl-4-aminophenol or 3,5-dibromaminophenol; Pyrocatechol or derivatives thereof such as 4-cyclohexyl pyrocatechol, 3-methoxy pyrocatechol and 4- (N-octadecylamino) pyrocatechol; Phenylenediamine developers such as N, N-diethyl-p-phenylenediamine, 3-methyl-N, N-diethyl-p-phenylenediamine, 3-methoxy-N-ethyl-N-hydroxyethyl-N, N-diethyl-p-phenylenediamine, 3-methoxy-N-ethyl-N-hydroxyethyl
• photographic developers of the 3-pyrazolidone type e.g. 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4,4-bis (hydroxymethyl) -3-pyrazolidone, 1,4-dimethyl-3-pyrazolidone, 4-methyl-3-pyrazolidone, 4, 4-dimethyl-3-pyrazolidone, 1- (3-chlorophenyl) -4-methyl-3-pyrazolidone, 1- (4-chlorophenyl) -4-methyl-3-pyrazolidone, 1- (3-chlorophenyl) -3- pyrazolidone, 1- (4-chlorophenyl) -3-pyrazolidone, 1- (4-chlorophenyl) -3-pyrazolidone, 1- (4-chlorophenyl) -3
• the photographic developers can be fed to the reaction mechanism in the photographic material in various ways. For example, they can be added to the developer liquid and used with it in the usual way. They can also be added in whole or in part to one or more layers of the photographic material, for example one or more of the photosensitive materials Lich silver halide emulsion layers, auxiliary layers, intermediate layers or image-receiving layers.
• the imagewise distribution of the diffusing dye released during development corresponds to the imagewise distribution of the undeveloped silver halide
• conventional negative emulsions can be used .
• These can be chemically or spectrally sensitized in a known manner and can contain the usual emulsion additives, such as stabilizers, curing agents, wetting agents, oil formers and the like.
• a photosensitive element which contains one or more silver halide emulsion layers and the associated non-diffusing coloring compounds and an image receiving element in which the desired color image is generated by the imagewise transferred diffusing dyes.
• This requires that there be firm contact between the photosensitive member and the image-receiving member for at least a finite period within the development time, so that the imagewise distribution of diffusing dyes generated in the photosensitive member as a result of the development passes to the image-receiving member can be worn.
• the contact can be made after development has started or it can have been made before development begins.
• the mono-sheet material can be composed in such a way that two different parts are produced separately from one another, namely the light-sensitive part (layer elements 1 to 4) and the cover sheet (layer elements 5 to 7), which are then placed on top of one another on the layer side and connected to one another, if necessary under Use of spacer strips so that a space is formed between the two parts for receiving a precisely measured amount of a working fluid.
• the layer elements 5 and 6, which together form the neutralization system, can also be arranged additionally or alternatively - but in the opposite order - between the layer support and the image-receiving layer of the light-sensitive part.
• Means may be provided to introduce a developer or activator liquid between the photosensitive member and the cover sheet, e.g. in the form of a laterally arranged, splittable container which, when subjected to mechanical forces, pours its contents between two adjacent layers of the mono-sheet material.
• An essential part of the photographic recording material according to the present invention is the photosensitive element which, in the case of a single dye transfer process, contains a photosensitive silver halide emulsion layer and, associated therewith, a non-diffusing coloring compound according to the invention.
• the non-diffusing Compound in a layer adjacent to the silver halide emulsion layer or in the silver halide emulsion layer itself, in the latter case the color of the image dye is preferably selected so that the predominant absorption range of the coloring compound does not match the predominant sensitivity range of the silver halide emulsion layer.
• the light-sensitive element contains three such assignments of coloring compound and light-sensitive silver halide emulsion layer, the absorption range of the coloring compound generally matching the range of spectral sensitivity of the associated silver halide emulsion layer, and according to the present invention at least one of the coloring compounds is a non-diffusing reducible compound according to the invention.
• the color-providing compound is arranged in a separate binder layer (seen in the direction of the light incident during the exposure) behind the silver halide emulsion layer.
• the developer oxidation products resulting from the development of a silver halide emulsion may differ of course, only affect the assigned coloring connection. Separating layers are therefore generally present in the photosensitive element, which effectively prevent the diffusion of the developer oxidation products into other unassigned layers.
• the silver halide emulsion layers can also be arranged in a different order, but the assigned layers with the color giving systems must also be interchanged so that the respective assignments are retained.
• the opaque layer arranged under the photosensitive element is permeable to aqueous alkaline treatment solutions and thus to the diffusing dyes. It essentially has two functions: firstly, it serves to cover the image silver remaining in the originally light-sensitive element after development, as well as the color-providing compounds remaining as color negatives, so that when viewed through the transparent substrate of the light-sensitive part, only the positive color transfer image is visible ; second, it closes the light-sensitive element in a light-tight manner on the side of the image-receiving layer (downward).
• the latter is particularly important if, after exposure, the mono-sheet material is still brought into contact with the alkaline processing compound in the camera, then is to be pulled out of the camera and developed outside the camera.
• Layers with sufficient opacity but sufficient permeability for diffusing dyes can be produced in a known manner with suspensions of inorganic or organic pigments, for example with suspensions of carbon black and / or Ti0 2 , in suitable binders, for example in gelatin solutions.
• means for producing such an opaque layer may also be provided between the photosensitive element and the image-receiving layer, e.g. in the form of a laterally arranged container with a working fluid containing an opacifying agent (pigment) which, when subjected to mechanical forces, pours its contents between the layers mentioned, so that such a pigment layer forms there.
• an opacifying agent pigment
• the image-receiving layer consists essentially of a binder which contains dye mordants for the determination of the diffusing dyes, e.g. non-diffusing monomeric or polymeric compounds with quaternary ammonium groups.
• the transparent layer support for the monosheet material As the transparent layer support for the monosheet material according to the invention, the usual transparent support materials used in photographic practice, e.g. Film made of cellulose esters, polyethylene terephthalate, polycarbonate or other film-forming polymers can be used.
• Film made of cellulose esters, polyethylene terephthalate, polycarbonate or other film-forming polymers can be used.
• Neutralization systems which are combinations of an acidic polymer layer and a retardation layer, are described, for example, in DE-PS 1 285 310.
• Such layer combinations can be present in the material according to the invention, for example in the light-sensitive part between the transparent layer support and the image-receiving layer.
• the neutralization system consisting of acidic polymer layer and retardation layer can also be arranged on the cover sheet.
• these two layers must be arranged in such an order that the developer alkali must first penetrate the retardation layer in order to get into the acidic polymer layer.
• the dye diffusion transfer process according to the invention can advantageously be carried out in or by means of a suitable self-developing camera.
• a suitable self-developing camera This can e.g. be provided with devices which, after exposure of the photosensitive element, make it possible to distribute a developer liquid between the latter and the cover sheet and to cover the photosensitive material in an opaque manner.
• Such a camera is preferably provided with two nip rollers mounted against one another, between which the mono-sheet material is pulled out, the laterally arranged containers being split up and releasing their contents between the layers of the mono-sheet material.
• the exposed material can be pulled out of the camera immediately after starting development.
• the imagewise exposed photosensitive element is brought into contact with the aqueous alkaline developer liquid.
• the imagewise exposed silver halide emulsion layers are developed in the presence of the developer compound, an imagewise distribution of oxidation products of the developer compound which oxidizes the associated ED compound and thus removing the subsequent reaction with the reducible compound according to the invention being produced in accordance with the silver image formed in the process; the remaining pictorial distribution (residual image) of ED compound reduces the reducible coloring compound according to the invention in its reduced form; from which the diffusing dye is split off under the action of the activator or developer alkali.
• the aqueous alkaline developer liquid can contain viscosity-increasing additives, e.g. Hydroxyethyl cellulose. Furthermore, it can contain development accelerators, stabilizers, silver salt solvents, fogging agents, antioxidants and other additives in a known manner.
• viscosity-increasing additives e.g. Hydroxyethyl cellulose.
• it can contain development accelerators, stabilizers, silver salt solvents, fogging agents, antioxidants and other additives in a known manner.
• the photographically active group is a diffusing dye or diffusing dye Is dye precursor.
• the photographically active group is, for example, an antifoggant, a development inhibitor, a hardening agent, a developing agent or an accelerating agent.
• the photographically active group is released imagewise, ie in accordance with the imagewise distribution of undeveloped silver halide when using negative emulsions. This opens up a wide range of possibilities for image generation.
• a pickling layer, a light-reflecting layer and a light-sensitive silver halide emulsion layer were applied to a transparent cellulose triacetate support in the following order.
• a slurry of 42 g of TiO 2 in 20 ml of water was dispersed in 150 ml of 8% aqueous gelatin solution with the addition of 5 ml of 5% aqueous solution of sodium dodecylbenzenesulfonate and 5 ml of 5% aqueous saponin solution. After adding 1 ml of 2% mucochloric acid solution, the dispersion was adjusted to a viscosity of 13 mPa.s at 40 ° C. and applied to the dried pickling layer by immersion (casting speed 5 m / min).
• each of the compounds I listed in the table below and 3.75 mmol of the ED compounds were dissolved in 25 ml of ethyl acetate and dispersed in 100 ml of a 5% gelatin solution with the addition of 5 ml of lauric acid diethylamide. After further addition of 100 ml of 5% gelatin and 3 ml of 2% mucochloric acid solution, each of the dispersions was mixed with 50 g of a ready-to-pour silver halide emulsion.
• This silver halide emulsion was prepared with 74 g A G NO 3 per kg emulsion; it had an Ag / gelatin ratio of 1: 1.1 and the halide was mainly bromide with 0.67 mol% iodide.
• the mixtures were applied to the dried light-reflecting layer using the dipping method at a speed of 5 m / min at 40 ° C.
• the content of a bag which is customary in diffusion transfer processes was applied to the exposed material obtainable in exemplary embodiment 1.
• the liquid released contained, based on 1 l of aqueous solution, the following chemicals:

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1980
  • 1980-04-16 DE DE19803014669 patent/DE3014669A1/de not_active Withdrawn
• 1981
  • 1981-04-03 EP EP81102517A patent/EP0037985B1/fr not_active Expired
  • 1981-04-03 DE DE8181102517T patent/DE3160429D1/de not_active Expired
  • 1981-04-09 US US06/252,572 patent/US4381339A/en not_active Expired - Fee Related
  • 1981-04-14 CA CA000375471A patent/CA1163991A/fr not_active Expired
  • 1981-04-14 JP JP5514481A patent/JPS56165144A/ja active Pending

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